KR20190058495A - Resin composition, pellet, bale, damping material, sound insulating material and interlayer for laminated glass - Google Patents

Abstract

A resin composition, a pellet, a bale, a damping material, a sound insulating material and an interlayer for laminated glass. Specifically, the resin composition is a resin composition containing the following block copolymer or its hydrogenated product (X) and a tackifier resin (Y) having a glass transition temperature of -50 to 45 캜, Wherein Tg (X) and Tg (X) represent the glass transition temperature of the polymer block (B) of the hydrogenation product (X) and the glass transition temperature of the tackifier resin (Y) Y) is 50 DEG C or less. Block copolymer or hydrogenated product thereof (X): A polymer block (A) containing at least 70 mol% of a structural unit derived from an aromatic vinyl compound and at least one member selected from the group consisting of a conjugated diene compound and isobutylene (A) in the block copolymer is 25% by mass or less as a block copolymer or a hydrogenated product thereof having a polymer block (B) containing at least 30 mol% of derived structural units, Or a hydrogenated product thereof.

Description

Resin composition, pellet, bale, damping material, sound insulating material and interlayer for laminated glass

The present invention relates to a resin composition, a pellet, a bale, a damping material, a sound insulating material and an interlayer for a laminated glass.

It is already known that a block copolymer having a polymer block containing a structural unit derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from a conjugated diene compound and a hydrogenated product thereof are excellent in vibration damping property, The resin composition has been used as a vibration damping material.

In recent years, it has become an important issue to reduce noise and vibration caused by low vibration inside the vehicle such as automobiles, low noise, spread of office equipment in general households, and large-sized household appliances. Even in the case of bridges and other structures, industrial machines and the like are being made to have low vibration and low noise. For this reason, there is a demand for the development of materials having even better vibration damping properties.

As materials excellent in vibration damping properties, the following (i) to (iv) are known.

(I) at least one kind selected from the group consisting of an elastomer (A), a softening agent (B), a tackifier (C) and a plasticizer (D), and the loss tangent (see Patent Document 1) in which the peak of tan delta is 20 占 폚 or less, the loss tangent (tan?) is 0.4 or more at 20 占 폚, and the storage elastic modulus (G ') at 20 占 폚 is 1 MPa or less. ,

(Ii) a block composed of a vinyl aromatic monomer having at least two predetermined number average molecular weights in the molecule and a block copolymer comprising isoprene or isoprene-isoprene having at least one vinyl bond metal flow rate of 40% or more and a peak of main dispersion of tan? Butadiene, and 5 to 250 parts by weight of a tackifier resin having a softening point of 30 占 폚 or higher (see Patent Document 2); and a composition comprising 100 parts by weight of a block copolymer having a predetermined molecular weight,

(Iii) a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising at least one of (A) a polymer block composed mainly of a vinyl aromatic compound and a polymer block composed mainly of a conjugated diene compound, and (B) 1 to 500 parts by mass of oil as a softening agent, and (C) 0.1 to 50 parts by mass of a polyolefin resin as a processing aid, and further contains (D) a viscoelasticity adjusting resin, An impact absorbing material comprising an elastomer composition having a C hardness of 10 to 70 degrees (see Patent Document 3)

(A) a block (A) comprising at least one vinyl aromatic monomer and comprising a block (A) having a predetermined number average molecular weight and isoprene, butadiene or isoprene-butadiene, A block copolymer having a number average molecular weight of 30% or more, a peak temperature of tan? Of -20 占 폚 or more and a peak value of tan? Of 0.3 or more, or a hydrogenated product thereof, (b) 10 to 2,000 parts by weight of a softening agent, and (c) 10 to 2,000 parts by weight of a tackifier resin (see Patent Document 4).

Japanese Laid-Open Patent Publication No. 2006-335997 Japanese Patent Application Laid-Open No. 02-135256 Japanese Patent Application Laid-Open No. 2010-275457 Japanese Laid-Open Patent Publication No. 06-293853

According to the examination by the present inventors, in any of the prior arts, sufficient vibration damping property is not necessarily obtained. Therefore, it is required to develop a technique for improving the vibration damping property of the block copolymer or its hydrogenation product more efficiently and more effectively.

Accordingly, an object of the present invention is to provide a resin composition, a pellet, a bale, a vibration damper, a sound insulating material and an interlayer for laminated glass, which is further superior in vibration damping property.

In order to solve the above problems, the inventors of the present invention have conducted intensive studies, and as a result, have found that when a specific block copolymer or its hydrogenation product and a tackifier resin having a predetermined glass transition temperature It has been found that the vibration damping property is greatly improved when the temperature is lower than the predetermined temperature and the present invention has been accomplished.

The present invention relates to the following [1] to [22].

[1] A resin composition comprising the following block copolymer or hydrogenated product thereof (X) and a tackifier resin (Y) having a glass transition temperature of -50 to 45 캜,

When the glass transition temperature of the polymer block (B) of the block copolymer or the hydrogenated product (X) is Tg (X) and the glass transition temperature of the tackifier resin (Y) is Tg (X) and Tg (Y) is 50 DEG C or less.

Block copolymer or hydrogenated product thereof (X): A polymer block (A) containing at least 70 mol% of a structural unit derived from an aromatic vinyl compound and at least one member selected from the group consisting of a conjugated diene compound and isobutylene (A) in the block copolymer is 25% by mass or less as a block copolymer or a hydrogenated product thereof having a polymer block (B) containing at least 30 mol% of derived structural units, Or a hydrogenated product thereof.

[2] The resin composition according to the above [1], wherein the tackifier resin (Y) has a molecular weight of 100 to 10,000.

[3] The resin composition according to [1] or [2], wherein the tackifier resin (Y) has an alicyclic skeleton.

[4] The resin composition according to [1] or [2], wherein the tackifier resin (Y) contains an oxygen atom.

[5] The resin composition according to any one of [1] to [4], wherein the tackifying resin (Y) has an acid value of 100 mgKOH / g or less.

[6] The resin composition according to any one of [1] to [5], wherein the tackifier resin (Y) is at least one selected from the group consisting of a rosin resin, a phenol resin and a coumarone- .

[7] The resin composition according to the above [6], wherein the rosin-based resin is a hydrogenated or nonhydrogenated rosin ester.

[8] The resin composition according to any one of [1] to [7], wherein the tackifier resin (Y) is a liquid at 25 ° C.

[9] The resin composition according to any one of the above [1] to [8], wherein the block copolymer or the hydrogenated product thereof (X) has a weight average molecular weight of 20,000 to 800,000.

[10] The resin composition according to any one of the above [1] to [9], wherein the hydrogenation degree of the hydrogenation product in the polymer block (B) is 80 to 99 mol%.

[11] The resin composition according to any one of [1] to [10], wherein in the block copolymer or the hydrogenated product (X), the conjugated diene compound is a mixture of isoprene, butadiene or isoprene and butadiene.

[12] The resin composition according to any one of [1] to [11], wherein the content of the polymer block (A) in the block copolymer is 1 to 15 mass%.

[13] The resin composition according to any one of the above [1] to [12], wherein the content ratio [X / Y] of the component (X) and the component (Y) is 90/10 to 10/90 by mass ratio.

(14) The morphology of a 1 mm-thick film obtained by molding the block copolymer or the hydrogenated product (X) thereof according to the following molding conditions has a spherical micro-phase separation structure. 13].

Molding conditions: Press at a temperature of 200 캜 and a pressure of 10 MPa for 3 minutes.

[15] The resin composition according to any one of [1] to [14], wherein the morphology of the film having a thickness of 1 mm obtained by molding the resin composition according to the following molding conditions has a spherical micro- .

Molding conditions: Press at a temperature of 200 캜 and a pressure of 10 MPa for 3 minutes.

The ratio [G '(-)] of the storage elastic modulus G' (-5) at the peak top temperature -5 ° C. to the storage modulus G '(top) at the peak top temperature of tan δ of the resin composition, 5] / G '(top)] is 10 or more.

According to JIS K7244-10 (2005), the peak top strength of tan? Measured at a strain of 0.1%, a frequency of 1 Hz, a measurement temperature of -70 to 200 占 폚 and a temperature rise rate of 3 占 폚 / , And the resin composition according to any one of the above [1] to [16].

[18] A pellet comprising the resin composition according to any one of [1] to [17].

[19] A veil comprising the resin composition of any one of [1] to [17].

[20] A vibration damper comprising the resin composition according to any one of [1] to [17].

[21] A sound insulating material comprising the resin composition according to any one of [1] to [17].

[22] An interlayer for laminated glass comprising the resin composition of any one of [1] to [17].

According to the present invention, it is possible to provide a resin composition, a pellet, a bale, a damping material, a sound insulating material and an interlayer film for a laminated glass, which is further excellent in vibration damping property.

1 is a schematic diagram of a micro-phase separation structure of a sphere.
2 is a schematic view of a micro-phase separation structure of a cylinder.
Figure 3 is a schematic diagram of a micro-phase separation structure of a lamella.
4 is a graph showing the relationship between the storage elastic modulus G '(top) of the peak top temperature tan δ of the resin composition and the storage modulus G' (-5) of the peak top temperature -5 ° C. [G ' ) / G '(top)].

The present invention relates to a block copolymer or a hydrogenated product thereof (hereinafter sometimes referred to as component (X)) which will be described later, and a tackifier resin (Y) having a glass transition temperature of -50 to 45 캜 (Hereinafter referred to as " Y "),

When the glass transition temperature of the polymer block (B) of the block copolymer or the hydrogenated product (X) is Tg (X) and the glass transition temperature of the tackifier resin (Y) is Tg (X) and Tg (Y) is 50 DEG C or less.

Hereinafter, the absolute value of the difference between Tg (X) and Tg (Y), that is, | Tg (X) - Tg (Y) | may be represented by |? Tg |.

If | Tg | exceeds 50 占 폚, the effect of improving the vibration damping property can not be obtained. In view of the vibration damping property, |? Tg | is preferably 45 占 폚 or lower, more preferably 40 占 폚 or lower, still more preferably 30 占 폚 or lower, particularly preferably 20 占 폚 or lower. The lower limit value of |? Tg | is not particularly limited and may be 0 占 폚 or 0.5 占 폚. The storage modulus G '(top) at the peak top temperature of tan? Of the resin composition described below is lower than the storage modulus G' (top) at the peak top temperature of the resin composition described below, because the component (X) (-5) / G '(top)] of the storage elastic modulus G' (-5) at the peak top temperature -5 ° C is increased and the peak intensity of tan? The vibration damping property of the component (X) can be greatly improved. In other words, the vibration damping property of the resin composition containing the component (X) and the component (Y) in which the value of |? Tg | falls within the above range, compared with the vibration damping property of only the component (X)

In the present invention, the glass transition temperature was determined according to the method described in the examples, specifically, the following measurement methods.

(Method of measuring glass transition temperature)

The component (X) was quenched using a differential scanning calorimeter "DSC6200" (manufactured by Seiko Instruments Inc.), and the temperature was elevated from -120 ° C. to 60 ° C. at a temperature raising rate of 10 ° C./min. And the glass transition temperature [Tg (X)] of the polymer block (B) was read.

The component (Y) was quenched by using a differential scanning calorimeter "DSC6200" (manufactured by Seiko Instruments Inc.), and the temperature was raised from -120 ° C. to 100 ° C. at a temperature raising rate of 10 ° C./min. The temperature was read to obtain the glass transition temperature [Tg (Y)] of the component (Y).

Hereinafter, the component (X) and the component (Y) contained in the resin composition of the present invention will be described in order.

[Block copolymer or hydrogenated product thereof (X)]

The component (X) is obtained by copolymerizing a polymer block (A) containing more than 70 mol% of a structural unit derived from an aromatic vinyl compound and a structural unit derived from at least one member selected from the group consisting of a conjugated diene compound and isobutylene And a polymer block (B) containing 30 mol% or more of a block copolymer or a hydrogenated product thereof, wherein the content of the polymer block (A) in the block copolymer is 25 mass% or less.

As the component (X), one type may be used alone, or two or more types may be used in combination.

(Polymer block (A))

The polymer block (A) contains more than 70 mol% of a structural unit derived from an aromatic vinyl compound (hereinafter may be abbreviated as "aromatic vinyl compound unit"), and from the viewpoint of mechanical properties, preferably 80 mol , More preferably 85 mol% or more, still more preferably 90 mol% or more, particularly preferably 95 mol% or more, and substantially 100 mol%.

Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,? -Methylstyrene,? -Methylstyrene, 2,6-dimethylstyrene, methylstyrene,? -methylstyrene,? -methylstyrene,? -methylstyrene,? -methylstyrene,? -methylstyrene,? -methyl- p-methylstyrene, 2,4,6-trimethylstyrene,? -methyl-2,6-dimethylstyrene,? -methyl-2,4-dimethylstyrene,? -methyl-2,6-dimethylstyrene, Chlorostyrene,? -Chlorostyrene,? -Chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, chlorostyrene,? -chloro-p-chlorostyrene,? -chloro-o-chlorostyrene,? -chloro-m-chlorostyrene,? -chloro-p- ,? -chloro-2,6-dichlorostyrene,? -chloro-2,4-dichlorostyrene,? -cl Butylstyrene, m-butylstyrene, pt-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methylstyrene, Bromomethylstyrene, p-bromomethylstyrene, a styrene derivative substituted with a silyl group, an organic acid such as indene , Vinyl naphthalene, and the like. The aromatic vinyl compound may be used singly or in combination of two or more kinds. Among them, styrene,? -Methylstyrene, p-methylstyrene, and a mixture thereof are preferable from the viewpoint of production cost and balance of physical properties, and styrene is more preferable.

However, the polymer block (A) may contain a structural unit derived from an unsaturated monomer other than an aromatic vinyl compound (hereinafter sometimes abbreviated as " another unsaturated monomer unit ") unless it interferes with the object and effect of the present invention. May be contained in an amount of 30 mol% or less. Examples of the other unsaturated monomer include butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methylvinylether, N- Vinylcarbazole,? -Pinene, 8,9-p-mentylene, dipentene, methylene norbornene, 2-methylene tetrahydrofuran, and the like. The content of the structural unit derived from the other unsaturated monomer in the polymer block (A) is preferably 20% by mole or less, more preferably 10% by mole or less, still more preferably 5% by mole or less, Substantially 0 mole%.

When the polymer block (A) contains the other unsaturated monomer unit, the bonding form is not particularly limited and may be either random or tapered.

The block copolymer may contain at least one of the polymer blocks (A). When the block copolymer has two or more polymer blocks (A), the polymer blocks (A) may be the same or different. In the present specification, " the polymer blocks are different " means that the monomer units constituting the polymer block, the weight average molecular weight, the stereoregularity, and the ratio of each monomer unit and the form of copolymerization Random, gradient, block).

The weight average molecular weight (Mw) of the polymer block (A) of the block copolymer is not particularly limited, but it is preferable that at least one polymer block (A) in the polymer block (A) Is preferably from 3,000 to 60,000, and more preferably from 4,000 to 50,000. By having the block copolymer have at least one polymer block (A) having a weight average molecular weight within the above range, the mechanical strength is further improved.

The "weight average molecular weight" described in the present specification and claims is all the weight average molecular weight in terms of standard polystyrene determined by Gel Permeation Chromatography (GPC). The weight average molecular weight of each polymer block (A) in the block copolymer can be determined by measuring the sampled solution each time polymerization of each polymer block in the production process is completed. For example, in the case of a triblock copolymer having an A1-B-A2 structure, the weight average molecular weight of the first polymer block (A1) and the polymer block (B) is determined by the above method, By subtracting them from the average molecular weight, the weight average molecular weight of the second polymer block (A2) can be obtained. As another method, in the case of a triblock copolymer having an A1-B-A2 structure, the total weight average molecular weight of the polymer block (A) is determined by the weight average molecular weight of the block copolymer and ¹ H-NMR measurement (A2) of the second polymer block (A2) by calculating the weight average molecular weight of the first polymer block (A1) deactivated by GPC measurement and subtracting the calculated weight average molecular weight from the total content of the polymer block .

The content of the polymer block (A) in the block copolymer (when the polymer block (A) has a plurality of polymer blocks (A), the total content thereof) is 25 mass% or less from the viewpoint of vibration damping property. If it exceeds 25% by mass, even if | Delta Tg | falls within the above range, the effect of improving the vibration damping property can not be obtained.

The lower limit of the content of the polymer block (A) is not particularly limited, but if the content of the polymer block (A) is less than 1% by mass, it tends to be difficult to form the block copolymer or the hydrogenated product (X) .

From the same viewpoint, the content of the polymer block (A) is preferably 1 to 25 mass%, more preferably 1 to 22 mass%, further preferably 1 to 18 mass%, and particularly preferably 1 to 15 mass% Mass%, 1 to 10 mass%, or 3 to 8 mass%. From the viewpoint of mechanical properties, the content is preferably 6 to 18 mass%, more preferably 6 to 15 mass%, still more preferably 8 to 15 mass%, and particularly preferably 10 to 15 mass%.

The content of the polymer block (A) in the block copolymer is a value determined by ¹ H-NMR spectrum, and more specifically, a value measured by the method described in the examples.

(Polymer block (B))

The polymer block (B) contains 30 mol% or more, preferably 50 mol% or more, and more preferably 65 mol% or more of a structural unit derived from at least one selected from the group consisting of a conjugated diene compound and isobutylene %, More preferably at least 80 mol%.

The polymer block (B) may contain a structural unit derived from a conjugated diene compound in an amount of 30 mol% or more, a structural unit derived from isobutylene in an amount of 30 mol% or more, and a conjugated diene compound and an isobutylene May contain at least 30 mol% of the structural units derived from the mixture of The polymer block (B) may have only a structural unit derived from one kind of conjugated diene compound, or may have a structural unit derived from two or more kinds of conjugated diene compounds.

Examples of the conjugated diene compound include isoprene, butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and myrcene. Among these, isoprene, butadiene, and a mixture of isoprene and butadiene are preferable, and any of them may be used. Of these, isoprene is more preferable. In the case of a mixture of butadiene and isoprene, the mixing ratio [isoprene / butadiene] (weight ratio) thereof is not particularly limited, but is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, 40/60 to 70/30, particularly preferably 45/55 to 65/35. When the mixing ratio [isoprene / butadiene] is represented by a molar ratio, it is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, further preferably 40/60 to 70/30, Particularly preferably 45/55 to 55/45.

As described above, the polymer block (B) preferably contains a structural unit derived from a conjugated diene compound in an amount of 30 mol% or more, and a structural unit derived from isoprene (hereinafter may be abbreviated as "isoprene unit" ) Is preferably contained in an amount of 30 mol% or more, more preferably 30 mol% or more of a structural unit derived from butadiene (hereinafter may be abbreviated as "butadiene unit"), a mixture of isoprene and butadiene (Hereinafter may be abbreviated as " a mixture unit of isoprene and butadiene " in some cases) of 30 mol% or more.

When the polymer block (B) has two or more kinds of structural units, their bonding form may be random, tapered, completely alternated, partially block-shaped, block, or a combination of two or more thereof.

When the constituent unit constituting the polymer block (B) is any of a mixture unit of an isoprene unit, a butadiene unit, an isoprene and a butadiene, in the case of the combination of isoprene and butadiene, 1,4-bond in case of isoprene, 1,2-bond, 3,4-bond and 1,4-bond in case of isoprene.

In the block copolymer, the sum of the content of the 3,4-bond unit and the 1,2-bond unit in the polymer block (B) (hereinafter sometimes referred to as the vinyl bond amount) is preferably at least 20 mol% , More preferably not less than 40 mol%, and still more preferably not less than 50 mol%. The amount of the vinyl bond in the polymer block (B) is preferably not more than 90 mol%, more preferably not more than 85 mol%, though not particularly limited. Here, the amount of vinyl bond is a value calculated by ¹ H-NMR measurement according to the method described in the examples.

When the polymer block (B) is composed of only butadiene, the above-mentioned "content of the 3,4-bonding unit and the 1,2-bonding unit" is changed to "content of the 1,2-bonding unit".

The total weight average molecular weight of the polymer block (B) of the block copolymer is preferably from 15,000 to 800,000, more preferably from 50,000 to 700,000 in the state before hydrogenation from the viewpoint of vibration damping property and the like , More preferably from 70,000 to 600,000, particularly preferably from 90,000 to 500,000, and most preferably from 130,000 to 450,000.

The polymer block (B) may contain a structural unit derived from a conjugated diene compound and other polymerizable monomers other than isobutylene, so far as the object and effect of the present invention are not impaired. In this case, the content of the structural unit derived from the polymerizable monomer other than the conjugated diene compound and isobutylene in the polymer block (B) is preferably less than 70 mol%, more preferably less than 50 mol% , More preferably less than 35 mol%, particularly preferably less than 20 mol%, and may be from 5 to 15 mol%.

Examples of the other polymerizable monomers include styrene,? -Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, vinylnaphthalene and vinyl anthracene And aromatic vinyl compounds such as methyl methacrylate, methyl vinyl ether, N-vinylcarbazole,? -Pinene, 8,9-p-mentene, dipentene, methylene norbornene, 2-methylene tetrahydrofuran, , At least one compound selected from the group consisting of 3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, and the like. Among them, styrene,? -Methylstyrene and p-methylstyrene are preferable, and styrene is more preferable.

When the polymer block (B) contains a structural unit derived from a conjugated diene compound and other polymerizable monomers other than isobutylene, a specific combination thereof is preferably a combination of isoprene, styrene, butadiene, styrene, isoprene, Butadiene and styrene, and more preferably is a mixture of isoprene and styrene, isoprene and butadiene, and styrene.

When the polymer block (B) contains a structural unit derived from a polymerizable monomer other than the conjugated diene compound and isobutylene, the bonding form thereof is not particularly limited and may be either random or tapered.

The block copolymer may have at least one of the polymer blocks (B). When the block copolymer has two or more polymer blocks (B), the polymer blocks (B) may be the same or different.

(The bonding pattern of the polymer block (A) and the polymer block (B)

As long as the polymer block (A) and the polymer block (B) are bonded to each other, the block copolymer is not limited in its bonding type, and may be any of linear, branched, radial, Either way. Among them, it is preferable that the polymer block (A) and the polymer block (B) are bonded in a linear form. For example, when the polymer block (A) is represented by A and the polymer block (B) A triblock copolymer represented by AB, a triblock copolymer represented by ABA or BAB, a tetrablock copolymer represented by ABAB, a pentablock copolymer represented by ABABA or BABAB, an (AB) nX copolymer (wherein X represents a coupling agent residue And n represents an integer of 3 or more). Among them, a linear triblock copolymer or a diblock copolymer is preferable, and an A-B-A type triblock copolymer is preferably used from the viewpoints of vibration damping property, flexibility, ease of manufacture, and the like.

Herein, in the present specification, when the same type of polymer block is bonded in a straight line via a bifunctional coupling agent or the like, the entire polymer block bonded is handled as one polymer block. Thus, including the above example, the polymer block, which should be denoted essentially as YXY (where X represents the coupling residue), is entirely different from the polymer block Y, Y. In this specification, this kind of polymer block containing the coupling agent moiety is handled as described above, for example, containing a coupling agent moiety and strictly indicated as ABXBA (X represents a coupling agent moiety) Is referred to as ABA and is treated as an example of a triblock copolymer.

In the present invention, the block copolymer (that is, the non-hydrogenated block copolymer) may be used as it is, or a hydrogenated product of the block copolymer (also referred to as a hydrogenated block copolymer) may be used.

From the viewpoints of heat resistance, weather resistance and vibration damping property, it is preferable that at least 80 mol% of the carbon-carbon double bonds of the polymer block (B) are hydrogenated (hereinafter sometimes abbreviated as hydrogenation) , More preferably at least 88 mol%, and still more preferably at least 88 mol%. Further, the value may be referred to as a hydrogenation rate (hydration rate). The upper limit value of the hydrogenation rate is not particularly limited, but the upper limit value may be 99 mol% or 98 mol%.

On the other hand, when considering crosslinking or foaming, the hydrogenation ratio may be 50 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, and further preferably 3 mol% or less.

The above hydrogenation rate is a value obtained by ¹ H-NMR measurement after hydrogenation of the content of the carbon-carbon double bond in the structural unit derived from the conjugated diene compound in the polymer block (B). More specifically, Is a value measured according to the method described in the examples.

(Weight average molecular weight (Mw) of the block copolymer or hydrogenated product (X) thereof)

The weight average molecular weight (Mw) of the block copolymer or its hydrogenated product (X) determined by gel permeation chromatography in terms of standard polystyrene is preferably 20,000 to 800,000, more preferably 50,000 to 700,000, 70,000 to 600,000, particularly preferably 90,000 to 500,000, and most preferably 130,000 to 450,000. When the weight average molecular weight of the block copolymer or its hydrogenated product (X) is 20,000 or more, the heat resistance is enhanced. When the weight average molecular weight is 800,000 or less, moldability is improved.

The block copolymer or its hydrogenation product (X) may contain a functional group such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group or an epoxy group in the molecular chain and / or the molecular end, One or more of them may be contained, or one having no functional group may be used.

(Morphology)

The morphology of the film having a thickness of 1 mm obtained by molding the block copolymer or the hydrogenated product (X) under the conditions of a pressure of 10 MPa and a pressure of 10 MPa for 3 minutes is not less than the sphere or sphericity It is preferable to have a micro-phase-separated structure of a cylinder (columnar) appearing in Fig. When the polymer block (A) is spherical and exists in the polymer block (B) and has a micro-phase separation structure in the cylinder (columnar phase), the polymer block And is present in the polymer block (B). The smaller the content of the polymer block (A) is, the more tendency is to have a micro-phase-separated structure of sphere.

The morphology of the film obtained by molding as described above has a micro-phase separation structure of spheres (sphere) or cylinder (columnar shape), so that vibration durability is further increased. From the same viewpoint, it is more preferable that the morphology of the film has a micro (spherical) phase separation structure.

Further, as shown in Fig. 3, when the film has a micro-phase separation structure of a lamellar structure in which a layer of the polymer block (A) and a layer of the polymer block (B) are alternately stacked, Do.

(Method for producing block copolymer or hydrogenated product (X) thereof)

The block copolymer or its hydrogenated product (X) can be produced by a solution polymerization method, an emulsion polymerization method or a solid phase polymerization method. Among them, a solution polymerization method is preferable, and known methods such as an ion polymerization method such as anion polymerization and cation polymerization, a radical polymerization method and the like can be applied. Among them, an anionic polymerization method is preferable. In the anion polymerization method, a block copolymer is obtained by sequentially adding at least one member selected from the group consisting of an aromatic vinyl compound and a conjugated diene compound in the presence of a solvent, an anionic polymerization initiator and, if necessary, a Lewis base , And if necessary, a coupling agent is added and reacted to obtain a desired block copolymer. If necessary, the hydrogenated block copolymer can be obtained by hydrogenating the block copolymer. In the cation polymerization method, for example, in the presence of a Lewis acid and an initiator system composed of an organic compound that forms a cationic polymerization active species in combination with the Lewis acid, optionally in the presence of an additive such as a pyridine derivative or an amide Can be produced by sequentially polymerizing monomers consisting mainly of an aromatic vinyl compound and monomers consisting mainly of isobutylene in an arbitrary order stepwise in an inert solvent such as hexane and methylene chloride to sequentially form the respective polymer blocks . Examples of the Lewis acid in this case include titanium tetrachloride, boron trichloride, aluminum chloride, and tin tetrachloride. Examples of organic compounds forming cationic polymerization active species include organic compounds having functional groups such as alkoxy groups, acyloxy groups and halogen atoms, and specific examples thereof include bis (2-methoxy-2-propyl) Benzene, bis (2-acetoxy-2-propyl) benzene and bis (2-chloro-2-propyl) benzene. Examples of the amide include dimethylacetamide, dimethylformamide, and the like.

Examples of the organic lithium compound which can be used as a polymerization initiator for anionic polymerization in the above method include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert- have. Examples of the di-lithium compound which can be used as a polymerization initiator include naphthalene di-lithium and dilithiohexylbenzene.

Examples of the coupling agent include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, and phenyl benzoate.

The amount of the polymerization initiator and the coupling agent is appropriately determined depending on the desired weight average molecular weight of the desired block copolymer or hydrogenated product thereof. Usually, the initiator such as an alkyl lithium compound and a dilithium compound is preferably used in a proportion of 0.01 to 0.2 part by mass per 100 parts by mass of the total amount of monomers such as aromatic vinyl compounds, butadiene, and isoprene, Is preferably used in a proportion of 0.001 to 0.8 part by mass per 100 parts by mass of the total amount of the monomers.

The solvent is not particularly limited as long as it does not adversely affect the anionic polymerization reaction. Examples of the solvent include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane and n-pentane; And aromatic hydrocarbons such as benzene, toluene and xylene. The polymerization is usually carried out at a temperature of 0 to 100 캜, preferably 10 to 70 캜 for 0.5 to 50 hours, preferably 1 to 30 hours.

In the case where the polymer block (B) of the block copolymer is a structural unit derived from a conjugated diene, the Lewis base is added as a cocatalyst at the time of polymerization, The content of the 1,2-bond can be increased.

Examples of the Lewis base that can be used include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, triethylamine, N, N , N ', N'-tetramethylenediamine, N-methylmorpholine, and the like. The Lewis base may be used singly or in combination of two or more species.

When the polymer block (B) contains a structural unit derived from a conjugated diene compound, in particular isoprene and / or butadiene, the amount of the Lewis base added is preferably such that the amount of the isoprene unit and / or the butadiene unit constituting the polymer block (B) And to what extent the amount of vinyl bonding is controlled. Therefore, although there is no strict restriction on the amount of the Lewis base added, it is usually 0.1 to 1,000 mol, preferably 1 to 100 mol, per 1 g of lithium contained in the alkyllithium compound or the dilithium compound used as the polymerization initiator It is preferable to use it within the range of molar amount.

After carrying out polymerization by the above-mentioned method, active hydrogen compounds such as alcohols, carboxylic acids and water are added to stop the polymerization reaction. Thereafter, when a hydrogenated block copolymer is obtained, a hydrogenation reaction (hydrogenation reaction) is carried out in an inert organic solvent in the presence of a hydrogenation catalyst. The hydrogenation reaction is carried out at a hydrogen pressure of 0.1 to 20 MPa, preferably 0.5 to 15 MPa, more preferably 0.5 to 5 MPa, a reaction temperature of 20 to 250 ° C, preferably 50 to 180 ° C, 70 to 180 ° C, and the reaction time is usually 0.1 to 100 hours, preferably 1 to 50 hours.

As the hydrogenation catalyst, for example, Raney nickel; Heterogeneous catalysts in which metals such as Pt, Pd, Ru, Rh, and Ni are supported on a single body such as carbon, alumina, or diatomaceous earth; A Ziegler-based catalyst comprising a combination of a transition metal compound, an alkyl aluminum compound, an alkyl lithium compound and the like; And metallocene catalysts.

The block copolymer or the hydrogenated product (X) thus obtained is solidified by pouring the polymerization reaction solution into methanol or the like, and then heated or reduced in pressure, or the polymerization reaction solution is poured in hot water together with steam and the solvent is azeotroped Followed by steam stripping, followed by heating or drying under reduced pressure.

[Adhesion-imparting resin (Y) having a glass transition temperature of -50 to 45 DEG C]

The resin composition of the present invention contains a tackifier resin having a glass transition temperature [Tg (Y)] of -50 to 45 ° C as the component (Y) together with the component (X). As the component (Y), one type may be used alone, or two or more types may be used in combination.

As the component (Y), among the known tackifier resins, those having a glass transition temperature of -50 to 45 占 폚 may be selected. In short, among the specific examples to be described later, those having the glass transition temperature can be used. The glass transition temperature of the component (Y) is preferably -50 to 15 占 폚, more preferably -40 to 0 占 폚, still more preferably -35 to -5 占 폚, particularly preferably -35 to -15 占 폚, and most preferably -35 to -20 占 폚. As the component (Y), a tackifier resin which is liquid at 25 占 폚 may be preferable.

However, in the present invention, since the tackifier resin is contained as the component (Y), the resin composition may be imparted with tackiness, but the component (Y) is not contained simply for imparting the tackiness, To further enhance the vibration damping property of the motor. In short, as described above, by selectively combining the component (X) and the component (Y) so that | DELTA Tg | satisfies the above range, the vibration damping property of the resin composition can be greatly increased.

The molecular weight of the component (Y) is not particularly limited, but is preferably 100 to 10,000, more preferably 100 to 5,000, still more preferably 150 to 3,000, particularly preferably 150 to 1,000, And most preferably from 200 to 600. By making the molecular weight of the component (Y) equal to or higher than the lower limit value, the bleed-out can be suppressed easily. By making the molecular weight not higher than the upper limit value, the glass transition temperature can be prevented from becoming excessively high.

From the viewpoint of vibration damping property, the acid value of the component (Y) is preferably 100 mgKOH / g or less, more preferably 60 mgKOH / g or less, still more preferably 30 mgKOH / g or less, / g or less, particularly preferably 3 mgKOH / g or less, and most preferably 1 mgKOH / g or less.

Here, the acid value may be referred to a catalog value if it is a commercial product, or it may be obtained by a potentiometric titration method according to JIS K0700 (1992).

Specific examples of the component (Y) include rosin resin, terpene resin, phenol resin, xylene resin, coumarone-indene resin, hydrogenated petroleum resin and styrene resin X) are excluded). As the component (Y), one type may be used alone, or two or more types may be used in combination. As the component (Y), a tackifier resin having an alicyclic skeleton is also a preferable embodiment. Also, a tackifier resin having an oxygen atom is also a preferred embodiment, and a tackifier resin having an alicyclic skeleton and an oxygen atom is also preferable. to be.

Among them, the component (Y) is preferably at least one member selected from the group consisting of a rosin-based resin, a phenol-based resin and a coumarone-indene-based resin, more preferably a rosin-based resin .

Examples of the rosin-based resin include rosins such as gum rosin, tall oil rosin, and wood rosin; Modified rosins such as hydrogenated rosin, disproportionated rosin, and polymerized rosin; Hydrogenated or nonhydrogenated rosin esters such as methyl esters, ethyl esters, propyl esters, glycerin esters and pentaerythritol esters, and the like, of ester compounds of these rosin or modified rosin and an alcohol can be mentioned. As the rosin-based resin, hydrogenated or unhydrogenated rosin ester is preferable from the viewpoint of vibration damping property. The ester moiety of the hydrogenated or unhydrogenated rosin ester is preferably methyl ester, ethyl ester or propyl ester from the viewpoint of lowering the glass transition temperature. As the rosin-based resin, a commercially available rosin-based resin may be used as it is, or it may be purified and used. It is also possible to use a specific organic acid (for example, abietic acid, neoabietic acid, palustric acid, pimaric acid, isopimaric acid, palustric acid, etc.) contained in the rosin- The species may be used singly or two or more species may be used in combination.

Examples of the terpene resin include terpene resins mainly composed of? -Pinene,? -Pinene and dipentene, aromatic modified terpene resins, hydrogenated terpene resins, and terpene phenol resins.

A (hydrogenated) petroleum resin, for example, (hydrogenated) aliphatic (C ₅ series) petroleum resin, (hydrogenated) aromatic (C ₉ series) petroleum resin, (hydrogenated) Aerial sum (C ₅ / C ₉ ) petroleum resin, (hydrogenated) dicyclopentadiene petroleum resin, and the like.

Examples of the styrene-based resin include poly-α-methylstyrene, α-methylstyrene / styrene copolymer, styrene monomer / aliphatic monomer copolymer, styrene monomer / α-methylstyrene / aliphatic monomer copolymer, Styrene-based monomer copolymer, styrene-based monomer / aromatic monomer copolymer, and the like.

From the viewpoint of compatibility with the component (X), it is preferable that the component (Y) is capable of showing peaks at 6 to 8 ppm in ¹ H-NMR measurement of the component (Y).

(Content ratio of component (X) to component (Y)

In the resin composition of the present invention, the content ratio [X / Y] of the component (X) and the component (Y) is preferably 90/10 to 10/90, more preferably 90/10 to 30 / 70, more preferably 80/20 to 30/70, even more preferably 80/20 to 40/60, particularly preferably 70/30 to 50/50, and most preferably 70/30 to 55/60. 45.

When the content ratio of the component (Y) is set to the predetermined amount or more, the effect of improving the vibration damping property tends to become sufficient. Further, by suppressing the content ratio of the component (Y) to a small value, it is possible to suppress deterioration of the mechanical properties and the moldability, and the component (Y) tends to suppress the bleed-out from the resin composition.

[Other components]

The resin composition of the present invention may contain components other than the above-mentioned component (X) and component (Y), if necessary. For example, it is possible to use various additives such as a softener, a filler, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a neutralizer, a lubricant, an antifog agent, an antifloccifier, a water repellent, a waterproofing agent, a colorant, Pigments and dyes such as antistatic agents, thermally conductive agents, electromagnetic shielding agents, crosslinking agents, crosslinking aids, crosslinking accelerators, foaming agents, foaming aids and processing aids.

As the softener, for example, mineral oil such as paraffinic process oil and naphthenic process oil; Vegetable oils such as peanut oil, rosin; Phosphate esters; Low molecular weight polyethylene glycols; Liquid paraffin; And synthetic oils such as low molecular weight ethylene, ethylene-? -Olefin copolymerized oligomers, liquid polybutene, liquid polyisoprene or hydrogenated products thereof, liquid polybutadiene or hydrogenated products thereof, and the like.

The resin composition of the present invention may contain a softening agent, but it is preferable that the resin composition does not affect the mechanism of manifesting the effect of the present invention. For example, 50 parts by mass More preferably not more than 40 parts by mass, further preferably not more than 30 parts by mass, particularly preferably not more than 10 parts by mass, and it is also preferable that the composition contains substantially no softening agent. This is because the glass transition temperature of the composition tends to decrease with an increase in the content of the softening agent, so that the tan? Peak top temperature to be described later decreases and the tan? Peak top frequency at 20 占 폚 increases so that the frequency And is not preferable when used as a vibration damping material, for example.

The resin composition of the present invention may contain other components in addition to the softening agent. However, it is preferable that the resin composition of the present invention has such a degree that it does not affect the mechanism of manifesting the effect of the present invention. For example, Is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and most preferably 10 parts by mass or less, based on the total amount of the other components (excluding the softening agent) Especially preferred are those in which substantially no other components are contained.

(Method for preparing resin composition)

The method for preparing the resin composition of the present invention is not particularly limited and can be prepared by using known means. For example, the components (X) and (Y) may be prepared by mixing, if necessary, other components using a mixer such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, a conical blender, , A single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, a roll, or the like at 80 to 250 ° C to prepare the resin composition of the present invention. It is also possible to prepare the resin composition by dissolving the respective components in a solvent in which each component (at least the component (X) and the component (Y)) is soluble and mixing and removing the solvent. In the case of preparing a resin composition composed of two kinds of the component (X) and the component (Y), the latter method is preferable because it is simple.

Further, in the case of foaming, for example, a resin composition obtained by dry-blending a foaming agent into a resin composition is obtained by injection-blow molding into a mold having a cavity having a desired shape.

(Pellets and veils)

The resin composition thus obtained (in particular, a resin composition which is not foamed) can be pelletized by means such as hot cut. It is also possible to form the bale by molding the resin composition with a bale-forming machine. In short, the present invention also provides a pellet or a veil containing the resin composition.

(peak top strength of tan delta)

A single-layer sheet having a thickness of 1.0 mm was prepared by pressing the resin composition of the present invention at a temperature of 200 캜 under a pressure of 10 MPa for 3 minutes, and the single-layer sheet was cut into a disc shape to obtain a test piece. Using the test piece, the peak top strength (tan δ) of tan δ measured under the conditions of a deformation amount of 0.1%, a frequency of 1 ㎐, a measuring temperature of -70 to 200 캜 and a heating rate of 3 캜 / min was measured according to JIS K7244-10 Can be at least 2.5, and therefore, the vibration damping property is excellent. The higher value may be 2.8 or more, 3.0 or more, 3.3 or more, or even 3.5 or more. The upper limit of the peak top strength of tan delta is not particularly limited, but tends to be 4.5 or less, and in many cases, it tends to be 4.2 or less.

It is also possible to prepare a test piece according to the above method using only the above-described component (X) in place of the resin composition, and determine the peak top strength of tan? The difference in strength (? Tan?) Preferably tends to be not less than +0.5, more preferably not less than +0.7, more preferably not less than +0.9, particularly preferably not less than +1.0, and when component (X) It can be said that the vibration damping property of the present resin composition is remarkably improved.

The peak top strength of tan? Is the value of tan? When the peak of tan? Is the maximum. The method of measuring the peak top strength of tan? is described in more detail in Examples.

The resin composition of the present invention has a storage elastic modulus G '(top) at the peak top temperature (-5 ° C) of the peak top temperature (-5 ° C) 5) / G '(top)] (corresponding to the slope 5 of the straight line connecting 3 and 4 in FIG. 4) More preferably 12 or more, more preferably 13 or more, and may be 14 or more or 15 or more in some cases. The upper limit of the ratio is not particularly limited, but is usually 20 or less. Here, the peak top temperature of tan? Is the temperature at which the peak of tan? Becomes the maximum. The numerical values in Fig. 4 are for reference, and are not affected at all by the numerical values described.

the polymer block (B) of the component (X) in the resin composition is softened in the temperature range from the peak top temperature of tan delta -5 deg. C to the peak top temperature of the delta delta, and the drop of the storage modulus G ' The slope 5 of the straight line connecting the 3 and 4 of 4 is large, the peak top strength of tan? Is improved and the effect of improving the vibration durability tends to be more conspicuous. In other words, in addition to the above-mentioned range of |? Tg | being in the above range, the effect of improving the vibration damping property tends to become more conspicuous when G '(-5) / G' (top) falls within the above range.

The storage elastic modulus is a value obtained by the following measurement method.

(Method of measuring storage elastic modulus)

A single-layer sheet having a thickness of 1.0 mm was prepared by pressing the resin composition of the present invention at a temperature of 200 캜 under a pressure of 10 MPa for 3 minutes, and the single-layer sheet was cut into a disc shape to obtain a test piece. The test piece is used to measure the storage elastic modulus in accordance with JIS K7244-10 (2005) under the conditions of a deformation amount of 0.1%, a frequency of 1 ㎐, a measuring temperature of -70 to 200 캜 and a heating rate of 3 캜 / min.

Here, the tan delta peak top temperature can be converted to the tan delta peak top frequency by the time temperature conversion rule. The tan? peak peak frequency corresponds to a frequency at which the vibration damping property can be exerted high when the resin composition is used as a vibration damping material.

The relationship between the tan? Peak top temperature at 1 Hz and the tan? Peak top frequency at 20 占 폚 is as follows.

&Quot; tan delta peak top temperature at 1 Hz " - tan? Peak top frequency at 20 deg. C; 20 캜 - 1 ㎐; 12 캜 - 10 ㎐; 3 캜 - 100 ㎐; -7 캜 - 1,000 ㎐; -10 캜 - 3,000 ㎐; -17 캜 - 10,000 Hz; -26 캜 - 100,000 ㎐; -36 ℃ - 1,000,000 ㎐

As described above, since the tan? Peak top frequency at 20 占 폚 increases with the decrease of the tan? Peak top temperature at 1 Hz, In order to use it as a crushing material, it is preferable to adjust the tan delta peak top temperature of the resin composition to an appropriate range.

Among them, in the case of using the resin composition of the present invention as an interlayer film for laminating glass, tan? At -10 DEG C to 3,000 Hz is important. The tan 隆 of the resin composition at -10 캜 is preferably 0.3 or more, more preferably 1.0 or more, still more preferably 1.5 or more, still more preferably 2.0 or more, particularly preferably 2.5 or more. When the resin composition has a tan δ at -10 ° C in the above range, it can effectively sound a high frequency region of 3,000 Hz or more when used in an interlayer film for laminated glass, thereby improving sound insulation.

The difference (tan delta) of the tan delta of the resin composition at -10 deg. C based on the tan delta at -10 deg. C of the component (X) is preferably 0 or more, more preferably + 0.1 or more, more preferably +0.3 or more, particularly preferably +0.5 or more.

The method of measuring tan? At -10 占 폚 is as described in the examples.

(Morphology of resin composition)

The resin composition of the present invention has a morphology of a film having a thickness of 1 mm obtained by molding under the conditions of a pressure of 10 MPa and a pressure of 10 MPa for 3 minutes and a morphology of a film having a micro-phase separation structure of a sphere (spherical) . The micro-phase separation structure of the morphology of the sphere or cylinder referred to here is the same as the micro-phase separation structure shown in Fig. 1 or Fig. 2 formed by the above-mentioned block copolymer or its hydrogenation product (X). Although not particularly limited, in the resin composition, the polymer block (A) of the component (X) becomes an island phase and tends to form a sphere or a cylinder (corresponding to 1 in FIG. 1 and FIG. 2) And the component (Y) is compatible with the polymer block (B) of the component (X) to form a sea phase (corresponding to 2 in FIG. 1 and FIG. 2).

The morphology of the film obtained by molding as described above has a micro-phase separation structure of spheres (sphere) or cylinder (columnar shape), so that vibration durability is further increased. From the same viewpoint, it is more preferable that the morphology of the film has a micro (spherical) phase separation structure.

Further, after the film is formed, the morphology is evaluated, but it is considered that the resin composition itself has the same morphology.

[Usage]

The resin composition of the present invention is excellent in vibration damping property. Therefore, the present invention also provides a damping material, a sound insulating material, a sound-absorbing material, an interlayer for laminated glass, etc., which contains the resin composition of the present invention. The vibration damper is preferably used particularly for a vibration damper for an automobile. In addition, dam rubber, shoe materials, floor materials, weather strips, floor mats, dash insulators, roof linings, door panels, engine head covers, door hole seals, fender liners and the like are also useful.

It is also possible to use various recorders, such as televisions, Blu-ray recorders and HDD recorders, projectors, game machines, digital cameras, home videos, antennas, speakers, electronic dictionaries, IC recorders, fax machines, IH cooking heater, hot plate, cleaner, washing machine, charger, sewing machine, ironing machine, dryer, electric bicycle, air purifier, water purifier, electric toothbrush, lighting equipment, air conditioner, microwave oven, microwave oven, refrigerator, dishwasher, An outdoor unit of an air conditioner, a dehumidifier, a humidifier, etc., it can be used as a sealing material, an adhesive, an adhesive, a packing, an O-ring, a belt,

In addition, all items described in this specification can be arbitrarily adopted. In short, it is possible to employ not only one item that is deemed desirable, but also a combination of items considered to be desirable and other items deemed desirable.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited at all by these examples.

Each measurement method in each example was carried out as follows.

[Method of Measuring Properties of Hydrogenated Block Copolymer]

(1) Content of polymer block (A)

The hydrogenated block copolymer was dissolved in CDCl ₃ and the ¹ H-NMR spectrum was measured (apparatus: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 50 ° C.) (A) was calculated.

(2) Morphology

The hydrogenated block copolymer was pressed at a temperature of 200 캜 and a pressure of 10 MPa for 3 minutes to produce a film having a thickness of 1 mm. The film was cut into a desired size to obtain a test piece, and then the surface was formed using a diamond cutter at a surface forming temperature of -110 캜. Using a scanning probe microscope (SPM) (manufactured by SII Ai Nanotechnology Co., Ltd.), the cross section of the test piece at a measurement temperature of 25 占 폚 was observed and the morphology was evaluated. Table 2 and Table 3 show the micro-phase separation structure of the sphere (Fig. 1), the cylinder (Fig. 2) and the lamella (Fig. 3).

(3) Weight average molecular weight (Mw)

The weight average molecular weight (Mw) of the hydrogenated block copolymer in terms of polystyrene was determined by Gel Permeation Chromatography (GPC) measurement under the following conditions.

(GPC measuring apparatus and measurement conditions)

Device: GPC device " HLC-8020 " (manufactured by Tosoh Corporation)

Separation column: "TSKgel GMHXL", "G4000HXL" and "G5000HXL" manufactured by Tosoh Corporation were connected in series.

Eluent: tetrahydrofuran

Eluent flow rate: 1.0 ml / min

Sample concentration: 5 mg / 10 ml

Column temperature: 40 ° C

Detector: differential refractive index (RI) detector

· Calibration curve: created using standard polystyrene

(4) Hydrogenation rate in polymer block (B)

The hydrogenation ratio in the polymer block (B) of the hydrogenated block copolymer was determined by ¹ H-NMR measurement.

Apparatus: Nuclear magnetic resonance apparatus "ADVANCE 400 Nano bay" (manufactured by Bruker)

Solvent: deuterated chloroform

(5) The amount of vinyl bond (the total content of 1,2-bond and 3,4-bond) of the polymer block (B) in the hydrogenated block copolymer,

¹ H-NMR measurement of the block copolymer before hydrogenation was carried out, and the 1,2-bond and the 3-bond of the sum of the peak areas of 1,2-bond and 3,4-bond and the peak area of 1,4- , And the ratio of the peak area of the 4-bond was calculated to obtain the amount of vinyl bond.

(6) The glass transition temperature [Tg (X)] of the polymer block (B)

The hydrogenated block copolymer was quenched using a differential scanning calorimeter "DSC6200" (manufactured by Seiko Instruments Inc.), and the temperature was elevated from -120 ° C. to 60 ° C. at a temperature raising rate of 10 ° C./min. Was read to obtain the glass transition temperature [Tg (X)] of the polymer block (B).

[Method of measuring physical properties of tackifier resin]

(7) acid value

The acid value of the tackifier resin was determined by the potentiometric titration method described in JIS K0700 (1992).

(8) Glass transition temperature [Tg (Y)]

The tackifier resin was quenched using a differential scanning calorimeter "DSC6200" (manufactured by Seiko Instruments Inc.), and the temperature was elevated from -120 ° C. to 100 ° C. at a temperature raising rate of 10 ° C./minute to read the temperature of the inflection point of the measurement curve , And the glass transition temperature [Tg (Y)] of the tackifier resin was determined.

(9) Weight average molecular weight

The weight average molecular weight of the tackifier resin was determined in the same manner as in the measurement of the weight average molecular weight of the hydrogenated block copolymer.

[Each component used in the examples]

Hereinafter, a method for producing a hydrogenated block copolymer used in Examples and Comparative Examples will be described.

(Production Example 1) Production of hydrogenated block copolymer (X-1)

50 kg of cyclohexane as a solvent and 20 g of a cyclohexane solution of sec-butyllithium having a concentration of 10.5% by mass as an anion polymerization initiator (a substantial addition amount of sec-butyllithium: 2.1 g), and 340 g of tetrahydrofuran as a Lewis base was introduced.

After the temperature inside the pressure-resistant container was raised to 50 캜, 0.16 kg of styrene (1) was added and the mixture was polymerized for 1 hour. Then, 7.8 kg of isoprene was added to polymerize for 2 hours. Further, 0.16 kg of styrene (2) To obtain a reaction solution containing a polystyrene-polyisoprene-polystyrene triblock copolymer.

A Ziegler-type hydrogenation catalyst formed of nickel octylate and trimethylaluminum was added to the reaction solution under a hydrogen atmosphere, and the reaction was carried out at a hydrogen pressure of 1 MPa and 80 DEG C for 5 hours. The reaction solution was cooled and purged, and then the catalyst was removed by washing with water, followed by vacuum drying to obtain a hydrogenated product of a polystyrene-polyisoprene-polystyrene triblock copolymer (hereinafter referred to as X-1) .

Table 1 summarizes each raw material and its usage. The physical properties of the hydrogenated block copolymer (X-1) are shown in Table 2 separately.

(Production Examples 2 to 9) Preparation of hydrogenated block copolymer

Hydrogenated block copolymers (X-2) to (X-8) and (X'-1) were prepared in the same manner as in Production Example 1 except that the respective components and the amounts used were changed as shown in Table 1 .

Properties of the respective hydrogenated block copolymers are shown in Table 2 and Table 3 separately.

The tackifier resins used in Examples and Comparative Examples are as follows. The physical properties of the tackifier resin are shown in Tables 2 and 3.

(Used tackifier resin)

Hydrogenated rosin methyl ester

Rosin methyl ester (non-hydrogenated)

Dimerone (manufactured by Yasuhara Chemical Co., Ltd.)

Regalez (registered trademark) 1018 (manufactured by Eastman)

Pine Crystal (registered trademark) KE-311 (manufactured by Arakawa Chemical Industries, Ltd.)

Arcon (registered trademark) P100 (manufactured by Arakawa Chemical Industries, Ltd.)

(Examples 1 to 12 and Comparative Examples 1 to 4) Preparation of resin composition

The hydrogenated block copolymer obtained in each Production Example and the tackifier resin shown in Table 2 or Table 3 were dissolved in toluene and mixed, and then toluene was volatilized to prepare a resin composition. Using the resin composition thus obtained, physical properties were evaluated according to the following measuring method. The results are shown in Tables 2 and 3.

The physical properties of the resin composition obtained in each example were evaluated as follows.

[Method of evaluating physical properties of resin composition]

(10) Morphology of resin composition

The resin composition was pressed at a temperature of 200 占 폚 and a pressure of 10 MPa for 3 minutes to produce a film having a thickness of 1 mm. Using the film, the morphology was evaluated in the same manner as in the measurement of the morphology of the hydrogenated block copolymer. Table 2 and Table 3 show the micro-phase separation structure of the sphere (Fig. 1), the cylinder (Fig. 2) and the lamella (Fig. 3).

(11) Measurement of tan?

For the following measurement, a single layer sheet having a thickness of 1.0 mm was prepared by adjusting the thickness to 1.0 mm when the toluene was volatilized. The single-layer sheet was cut into a disk shape and used as a test sheet.

The dynamic viscoelastic device "ARES-G2" (manufactured by Japan Aerospace Exploration Co., Ltd.) having a disk diameter of 8 mm was used as a parallel plate oscillation rheometer based on JIS K7244-10 (2005) Were used.

The gap between the two discs was completely filled with the test sheet, and the test sheet was subjected to vibration at a frequency of 1 Hz at a deformation rate of 0.1%, and the temperature was raised from -70 ° C to 200 ° C at a constant rate of 3 ° C / minute . The measurement was carried out in a nitrogen atmosphere. The temperature of the test sheet and the original plate were maintained until the measured values of the shear loss elastic modulus and the shear storage elastic modulus were no longer changed, and the maximum value of the peak intensities of tan? And tan? Strength). The larger the value, the better the vibration damping property.

(12) Δtanδ

The measurement was carried out in the same manner as in (11) above except that a hydrogenated block copolymer was used instead of the resin composition.

The peak width of the peak top strength of tan delta when the resin composition was used was determined on the basis of the peak top strength of tan delta when the hydrogenated block copolymer was used and the value was defined as the difference in peak top strength .

The increase in the tan delta when the resin composition was used was determined on the basis of the tan delta at -10 deg. C when the hydrogenated block copolymer was used, and the value of the increase in tan delta at -10 deg. (? Tan?).

Further, when the resin composition is used, tan δ is represented by plus (+), and when the resin composition is used, tan δ is represented by minus (-) when the value is smaller. The larger the value, the better the effect of improving the vibration damping property.

(13) The ratio of the storage elastic modulus G '(-5) to the storage modulus G' (top) at the peak top temperature of tan 隆 of the resin composition at the peak top temperature -5 ° C [G '(-5 ) / G '(top)]

The resin composition was pressed at a temperature of 200 占 폚 and a pressure of 10 MPa for 3 minutes to prepare a single-layer sheet having a thickness of 1.0 mm, and the single-layer sheet was cut into a disk shape to obtain a test piece. Using the test piece, the storage elastic modulus was measured according to JIS K7244-10 (2005) under the conditions of a deformation amount of 0.1%, a frequency of 1 Hz, a measurement temperature of -70 to 200 DEG C, and a temperature rise rate of 3 DEG C / min.

The storage elastic modulus G '(top) at the temperature (peak top temperature of tan?) At which the peak top strength of tan? Is obtained in (11) and the storage elastic modulus G' G '(- 5) / G' (top)] were calculated.

From Table 2 and Table 3, it can be seen that in Examples 1 to 12, the peak top strength of tan? Is high and the peak top strength of tan? When using only component (X) is significantly improved. In addition, since the resin composition has high tan δ at -10 ° C, it can be said that when the resin composition of the present invention is used for an interlayer film for a laminated glass, a high frequency region of 3,000 Hz or more can be effectively removed.

On the other hand, in the case of Comparative Examples 1 to 3 where | DELTA Tg | exceeded 50 DEG C, the peak top strength of tan? Of the resin composition was insufficient, and the peak top strength of tan? The improvement effect could not be seen, and the tendency to decrease was seen. In Comparative Example 4 using the hydrogenated block copolymer (X'-1) in which the content of the polymer block (A) exceeds 25% by mass, even though | ΔTg | is 50 ° C. or less, the tanδ The peak top strength of the hydrogenated block copolymer was insufficient and the effect of improving the peak top strength of tan? When only the hydrogenated block copolymer was used was not observed. In short, the effect of the present invention can be said to be an effect expressed when the content of the polymer block (A) is 25 mass% or less.

Industrial availability

The resin composition of the present invention is excellent in vibration damping property. Therefore, damping agents, sound insulating materials, sound absorbing materials, interlayer films for laminated glass, etc., containing the resin composition of the present invention are industrially useful. Further, in addition to the above, it is also possible to use a dam rubber, a shoe material, a floor material, a weather strip, a floor mat, a dash insulator, a roof lining, a door panel, an engine head cover, a door hole seal, It is industrially useful.

It is also possible to use various recorders, such as televisions, Blu-ray recorders and HDD recorders, projectors, game machines, digital cameras, home videos, antennas, speakers, electronic dictionaries, IC recorders, fax machines, IH cooking heater, hot plate, cleaner, washing machine, charger, sewing machine, ironing machine, dryer, electric bicycle, air purifier, water purifier, electric toothbrush, lighting equipment, air conditioner, microwave oven, microwave oven, refrigerator, dishwasher, An outdoor unit of an air conditioner, a dehumidifier, a humidifier, etc., it can be used as a sealing material, an adhesive, an adhesive, a packing, an O-ring, a belt, a soundproofing material and the like.

1: polymer block (A)
2: polymer block (B), or polymer block (B) and component (Y)
3: The storage elastic modulus G '(top) at the peak top temperature of tan?
4: the storage elastic modulus G '(-5) at the peak top temperature -5 ° C,
5: The slope represented by [G '(- 5) / G' (top)]

Claims (22)

(X) and a tackifier resin (Y) having a glass transition temperature of -50 to 45 占 폚,
When the glass transition temperature of the polymer block (B) of the block copolymer or the hydrogenated product (X) is Tg (X) and the glass transition temperature of the tackifier resin (Y) is Tg (X) and Tg (Y) is 50 DEG C or less.
Block copolymer or hydrogenated product thereof (X): A polymer block (A) containing at least 70 mol% of a structural unit derived from an aromatic vinyl compound and at least one member selected from the group consisting of a conjugated diene compound and isobutylene (A) in the block copolymer is 25% by mass or less as a block copolymer or a hydrogenated product thereof having a polymer block (B) containing at least 30 mol% of derived structural units, Or a hydrogenated product thereof. The method according to claim 1,
And the molecular weight of the tackifier resin (Y) is 100 to 10,000. 3. The method according to claim 1 or 2,
And the tackifier resin (Y) has an alicyclic skeleton. 3. The method according to claim 1 or 2,
And the tackifier resin (Y) contains oxygen atoms. 5. The method according to any one of claims 1 to 4,
And the acid value of the tackifier resin (Y) is 100 mgKOH / g or less. 6. The method according to any one of claims 1 to 5,
Wherein the tackifier resin (Y) is at least one selected from the group consisting of a rosin-based resin, a phenol-based resin and a coumarone-indene-based resin. The method according to claim 6,
Wherein the rosin-based resin is a hydrogenated or non-hydrogenated rosin ester. 8. The method according to any one of claims 1 to 7,
Wherein the tackifier resin (Y) is a liquid at 25 占 폚. 9. The method according to any one of claims 1 to 8,
Wherein the block copolymer or the hydrogenated product thereof (X) has a weight average molecular weight of 20,000 to 800,000. 10. The method according to any one of claims 1 to 9,
Wherein the hydrogenation rate of the polymer block (B) in the hydrogenation product is 80 to 99 mol%. 11. The method according to any one of claims 1 to 10,
Wherein the conjugated diene compound in the block copolymer or the hydrogenated product thereof (X) is a mixture of isoprene, butadiene, or isoprene and butadiene. 12. The method according to any one of claims 1 to 11,
Wherein the content of the polymer block (A) in the block copolymer is 1 to 15% by mass. 13. The method according to any one of claims 1 to 12,
Wherein the content ratio [X / Y] of the component (X) and the component (Y) is 90/10 to 10/90 by mass ratio. 14. The method according to any one of claims 1 to 13,
Wherein the morphology of the film having a thickness of 1 mm obtained by molding the block copolymer or the hydrogenated product thereof (X) according to the following molding conditions has a spherical micro-phase separation structure.
Molding conditions: Press at a temperature of 200 캜 and a pressure of 10 MPa for 3 minutes. 15. The method according to any one of claims 1 to 14,
Wherein the morphology of the film having a thickness of 1 mm obtained by molding the resin composition according to the following molding conditions has a micro-phase separation structure of a sphere (spherical shape).
Molding conditions: Press at a temperature of 200 캜 and a pressure of 10 MPa for 3 minutes. 16. The method according to any one of claims 1 to 15,
(G '(-5) / G') of the storage elastic modulus G '(-5) at the peak top temperature -5 ° C to the storage elastic modulus G' (top) at the peak top temperature of tan? G '(top)] is 10 or more. 17. The method according to any one of claims 1 to 16,
The peak top strength of tan? Measured at a strain of 0.1%, a frequency of 1 Hz, a measurement temperature of -70 to 200 占 폚, and a temperature rise rate of 3 占 폚 / min of 2.5 or more in accordance with JIS K7244-10 (2005) . A pellet comprising the resin composition according to any one of claims 1 to 17. 17. A veil comprising the resin composition according to any one of claims 1 to 17. 17. A vibration damper comprising the resin composition according to any one of claims 1 to 17. A sound insulating material comprising the resin composition according to any one of claims 1 to 17. An interlayer film for a laminated glass comprising the resin composition according to any one of claims 1 to 17.

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